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表面活性剂辅助组装纳米尺度锌配合物以增强水相串联转化反应

Surfactant-assisted assembly of nanoscale zinc coordination compounds to enhance tandem conversion reactions in water.

机构信息

Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou 450007, P. R. China.

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China.

出版信息

Dalton Trans. 2019 Nov 14;48(42):16008-16016. doi: 10.1039/c9dt03145f. Epub 2019 Oct 10.

Abstract

Precise control over the morphology and size of coordination polymers (CPs) is crucial for extending these inorganic-organic materials to many advanced applications, in particular for heterogeneous catalysis. In this work, two Zn-based CPs, {[Zn(idbt)(4,4'-dmbpy)]·HO} (1) and {[Zn(idbt)(HO)]·HO} (2) (Hidbt = 5,5'-(1H-imidazole-4,5-diyl)-bis-(2H-tetrazole), 4,4'-dmbpy = 4,4''-dimethyl-2,2'-bipyridine), were synthesized through solvothermal reactions. The morphologies and particle sizes of 1 and 2 could be controlled from large scale to nanoscale by regulating the amount of poly(vinyl alcohol) (PVA). Furthermore, for the conversion reactions of nitromethylbenzenes into benzoic acids, the catalytic properties of nanoscale 1 and 2 were much more efficient than those of large size of 1 and 2, because of the benefit of readily accessible active sites in the nanoscale sized particles, which provide a tunable and functionalizable platform for the conversion reaction by minimizing the diffusion distance but do little for the selectivity.

摘要

对配位聚合物 (CPs) 的形态和尺寸进行精确控制对于将这些无机-有机材料扩展到许多先进的应用中至关重要,特别是对于多相催化。在这项工作中,通过溶剂热反应合成了两种基于 Zn 的 CPs,{[Zn(idbt)(4,4'-dmbpy)]·HO} (1) 和 {[Zn(idbt)(HO)]·HO} (2) (Hidbt = 5,5'-(1H-咪唑-4,5-二基)-双-(2H-四唑),4,4'-dmbpy = 4,4''-二甲基-2,2'-联吡啶)。通过调节聚乙烯醇 (PVA) 的用量,可以将 1 和 2 的形貌和粒径从大尺寸控制到纳米尺寸。此外,对于将硝基甲苯转化为苯甲酸的转化反应,纳米尺寸的 1 和 2 的催化性能比大尺寸的 1 和 2 高得多,因为在纳米尺寸的颗粒中易于获得的活性位提供了一个可调谐且可功能化的转化反应平台,通过最小化扩散距离来提高反应效率,但对选择性影响不大。

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